Metal containing monoazo dyestuffs



United rates Patent if) ice METAL CONTAINING MONOAZO DYESTUFFS EdgarEnders, Leverkusen-Bayerwerk, Germany, assignor to Farbenfabriken BayerAktiengesellschaft, Leverkusen, Germany, a corporation of Germany NoDrawing. Application July 31, 1956 Serial No. 601,119

Claims priority, application Germany August 16, 1955 5 Claims. (Cl.260-146) The present invention relates to metal containing monoazodyestuffs and to a process for their manufacture; more particularly itrelates to the metal complexes of monoazo dyestuffs being free ofsulfonic and carboxylic acid groups and corresponding to the generalformula OH HO X wherein X means hydrogen or a non-ionic substituent, Rstands for an alkylsulfone or sulfonamide radical and R means a -CH CHCH radical linked to the 8- position of the carboxylic nucleus or Rstands for an alkyl-, aralkylor aryl-radical.

It is an object of the invention to provide new metal containing monoazodyestuffs with good fastness properties.

Monoazo dyestuffs of the above general formula are obtainable bycoupling diazotized 1-amino-2-hydroxybenzenes containing in the nucleusan alkyl-sulfone or an sulfonamide group which may be substituted andthe nucleus, if desired, being substituted by a further nonionicsubstituent, with 1,8-trimethylene-4-hydroxycarbostyril or withN-alkyl-, aralkylor aryl-4-hydroxy-2-quinolones.

Examples of suitable 1-amino-2-hydroxybenzenes are1-amino-2-hydroxybenzene-5-sulfonic acid amide,l-amino-2-hydroxybenzene-5-sulfonic acid methylamide, 1-amino-Z-hydroxybenzene-S-sulfonic acid dimethylamide,l-amino-2-hydroxybenzene-5-sulfonic acid anilide, l-amino 2hydroxybenzene S-methylsulfone, l-amino-2-hydroxybenzene-S-ethylsulfone,1-amino-2-hydroxybenzene- 4-sulfonic acid amide,1-amino-2-hydroxybenzene-4-sulfonic acid dimethylamide,1-amino-2-hydroxybenzene-4- sulfonic acid anilide,1-amino-2-hydroxybenzene-4-methylsulfone, 1 amino2-hydroxy-5-chlorobenzene-4-sulfonic acid amide, 1 amino2-hydroxy-5-methylbenzene-4-sulfonic acid amide,1-amino-2-hydroxy-3-nitrobenzene-5- sulfonic acid amide.

1,8-trimethylene-4-hydroxy-carbostyril used as coupling component mayreadily be obtained by heating tetrahydro-quinoline with malonic acidester (cf. Kayser and Reissert, Berichte der Deutschen ChemischenGesellschaft 25, 1193).

As coupling components there may be further used for exampleN-methyl-4-hydroxy-2-quinolone, N-ethyl-4-hydroxy 2 quinolone,N-butyl-4-hydroxy-2-quinolone, N- benzyl 4 hydroxy Z-quinolone,N-phenyl-4-hydroxy-2- quinolone.

The N-alkyl-, N-aralkylor N-aryl-4-hydroxy-2-quinolones may be prepared,for example, according to the instructions of German patentspecification No. 287,803 from the correspondingly substitutedanthranilic acids.

The metallisation of the monoazo dyestuifs may be 2,883,374 PatentedApr. 21, 1959 carried out by conventional processes, for instance, bythe action of chromium complexes of salicyclic acid, oxalic acid ortartaric acid, by the reaction with alkali metal chromates in thepresence of reducing agents, by heating with trivalent chromium salts inorganic solvents or by the action of ammoniacal solutions of cobaltsalts.

The metallisation may also be effected in mixture with knowno,o'-dihydroxyaz0 dyestuffs free from sulfonic acid groups or witho-hydroxy-o-aminoazo dyestuffs.

Metal-free dyestuifs of the said kind which exhibit a suflicientwater-solubility, may be converted on the fibre, for instance by thesingle bath chroming process, into their metal complex compounds.

The preferred azo dyestufis are, however, those metallised in substancewhich dye wool or materials of similar dyeing properties from a neutralto weakly acid bath in preponderantly red to reddish-brown shades. Thedyeings on wool thus obtained are distinguished by their good levellingproperties as well as by a very good fastness to washing, milling,decatizing and carbonizing and by an excellent fastness to light.

The following examples are given for the purpose of illustrating theinvention without, however, limiting it thereto. The parts by Weight andthe parts by volume stand in the ratio of grams to millilitres.

Example 1 11.0 parts by weight of 1-amino-2-hydroxy-benzene-5- sulfonicacid amide are stirred with 200 parts by volume of water and 12 parts byvolume of concentrated hydrochloric acid and diazotized with an aqueoussolution of 4.3 parts by weight of sodium nitrite. The suspension of thediazo compound is added with stirring to a solution of 11.7 parts byweight of 1,8-trimethylene-4-hydroxy-carbostyril in parts by volume of a15 percent soda solution, 15 parts by weight of a 40 percent sodiumhydroxide solution and parts by Weight of ice. After the coupling iscompleted, the mixture is heated to 70-80 C. and the dyestuff isseparated by addition of dilute acetic acid and filtered oif. Itcorresponds to the formula OaNHg O N I H2 CHZ'OH The dyestufi' pastethus obtained is dissolved in 500 parts by volume of water with additionof dilute sodium hydroxide and stirred with an ammoniacal solution of8.7 parts by weight of crystalline cobalt sulfate at 70-80" C. After themetallisation is terminated, the dyestuff is separated by the additionof common salt, pressed and dried. It is a brown powder which readilydissolves in water with a brown coloration and dyes wool from a neutralbath in level orange-brown shades of very good wet and light fastness.

For the preparation of the chromium complex, the paste of the metal-freedyestuff is dissolved with addition of dilute sodium hydroxide in 300parts by volume of water and heated under reflux with 200 parts byvolume of an alkaline solution of chromium salicylic acid, correspondingto 2.5 parts by weight of chromium oxide, until the metallisation isterminated. The separated and dried dyestuif is a reddish brown powderwhich readily dissolves in water with a bluish red coloration and dyes-wool from a neutral bath in level reddish bordo shades ofzene-4-sulfonic acid amide are stirred with 250 parts by volume of waterand 12 parts by volume of concentrated hydrochloric acid and diazotizedwith an aqueous solution of 4.3 parts by weight of sodium nitrite. Thesuspension. of the diazo compound is added with stirring to a solutionof 11.7 parts by weight of 1,8-trirnethylene- 4-hydroxy-carbostyril in100 parts by volume of a 15 percent soda solution, 15 parts by volume of40 percent sodium hydroxide and 150 parts by weight of ice. After thecoupling is completed, the mixture is heated to 70 80 C. and thedyestuif is separated by the addition of dilute hydrochloric acid andfiltered off. It corresponds to the formula OH 9H HzNOnS N 01 H: CH2.i111:

The dyestufi paste thus obtained is dissolved in 500 parts by volume ofwater with addition of dilute sodium hydroxide and stirring with anammoniacal solution of 8.5 parts by weight of crystalline cobalt sulfateat 70- 80 C. After the metallisation is terminated, the dyestuff isseparated by the addition of common salt, squeezed off and dried. It isa reddish brown powder which readily dissolves in water with a bluishred coloration and dyes wool from a neutral bath in level bluish redshades of very good wet and light fastness.

For the preparation of the chromium complex, the paste of the metal-freedyestuff is dissolved with the addition of dilute sodium hydroxide in500 parts by volume of water. While gently boiling the solution, aslightly alkaline solution of 6 parts by weight of sodium bichromate and6.5 parts by weight of glucose in 150 parts by volume of water is addeddropwise thereto. After the metallisation is completed, the dyestufl isisolated in conventional manner and dried. A brownish red powder isobtained which readily dissolves in water with a bluish red colorationand dyes wool from a neutral bath in level bordo shades of very good wetand light fastness.

In a similar manner the dyestuffs listed in the following table may beobtained.

Dyeing of Diazo component Coupling Metal the metal Component complex onwool 3 1-amino-2-hydroxy- 1,8-trimethylene O0 brick red.

benzene-ksulfonic 4-hydroxy-caracid amide. bostyril.

4 do do Or bluish red.

5 1-amin0-2-hydroxydo Cr Do.

' benzene-S-sultcnic acid dimethyl amide.

fi 1-amino-2-hydroxyd0 C0 brick red.

benzenel-sulfonic acid dimethyl amide.

7 do "do; Cr reddish claret.

8 1-amino-2hydroxy- .d0 O0 brick red.

benzeneA-sulfonic acid anilide.

9 do do Cr reddish claret.

10 1-amino-2-hydroxyorange benzene-S-methylbrown. sultone.

11 o ..do Gr bluish red.

12 1-arnino-2-hydroxydo Co brick red.

benzene-i-methylsulfone.

13 l-amino-zrhydroxyd0 Co orange benzene-5-ethylbrown. sulfone.

4 do Or bluish red.

15 l-amino-Z-hydroxy- .do Or Do.

benzene-5mpropyl-sulione.

4, Example 16 11.0 parts by weight of 1-amino-Z-hydroxybenzene-S-sulfonic acid amide are mixed with stirring with 200 parts by volume ofwater and 12 parts by volume of concentrated hydrochloric acid anddiazotized with an aqueous solution of 4.3 parts by weight of sodiumnitrite. The suspension of the diazo compound is added at 510 C. to asolution of 12.5 parts by weight of N-butyl-4-hydroxy-2-quinolone in 200parts by volume of water, 10 parts by volume of a 15 percent sodiumcarbonate solution. After the coupling is completed, the mixture isheated to 70-80 C., the dyestuff is separated out by addition of diluteacetic acid and filtered off. It corresponds to the formula OH OHSO2.NH7 O- N (EHz-CHz-CHg-CHG The dyestutf paste thus obtained isdissolved in 500 parts by volume of water with the addition of dilutesodium hydroxide and treated at C. with an ammoniacal solution of 8.5parts by weight of crystalline cobalt sulfate. After the metallisationis complete, the dyestuff is separated out by the addition of commonsalt, pressed and dried. It is a brown powder which readily dissolves inwater with a red-brown coloration and dyes wool from a neutral bath inlevel orange-brown shades of very good wet and light fastness.

For the preparation of the corresponding chromium complex, the solutionof the metal-free dyestuff is treated slowly at -100 C. with a weaklyalkaline solution of 5 parts by weight of sodium bichromate and 6 partsby weight of glucose in 50 parts by volume of water and worked up inusual manner after the metallisation is completed. A brown powder isobtained which readily dissolves in water with a red coloration and dyeswool from a neutral bath in level bluish red shades of very good wet andlight fastness.

Dyestuffs having similar properties are obtained by replacing the diazocomponent by an appropriate quantity of1-amino-2-hydroxybenzene-5-sulfonic acid methylamide,1-amino-2-hydroxybenzene-S-sulfonic acid anilide or1-amino-2-hydroxybenzene-5-sulfonic acid benzylamide, or by replacingthe coupling component by an appropriate amount ofN-methyl-4-hydroxy-2-quinolone.

Example 17 12.9 parts by weight of1-amino-2-hydroxy-5-chlorobenzene-4-sulfonic acid amide are stirred with250 parts by volume of water and 12 parts by volume of concentratcdhydrochloric acid and diazotized with an aqueous solution of 4.3 partsby weight of sodium nitrite. The suspension of the diazo compound iscombined with a solution of 12.5 parts by weight of N-butyl-4-hydroxy-2-quinolone in 200 parts by volume of water, 10 parts by volume of a 40percent sodium hydroxide solution and parts by volume of 15 percentsodium carbonate solution. After the coupling is completed, the mixtureis heated to 70-80 C., the dyestufi is separated by the addition ofdilute hydrochloric acid, filtered off and dried. It corresponds to theformula:

HgNOaS 1 dniorncntcrn filtered off and dried. A brown powder is obtainedwhich dissolves in water with a red coloration and dyes wool from aneutral bath in level bluish red shades of very good wet fastness andexcellent fastness to light.

1 The chromium complex of the same dyestuif dyes wool in reddish claretshades having likewise good fastness properties.

Example 18 11.0 parts by weight of 1-amino-2-hydroxybenzene-5- sulfonicacid amide are diazotized in conventional manner and combined with asolution of 6.2 parts by weight of N-butyl-4-hydroxy-2-quinolone and 5.8parts by weight of l-acetylamino-7-hydroxynaphthalene in 300 parts byvolume of water, 12 parts by volume of a 40 percent sodium hydroxidesolution and 100 parts by volume of a 15 percent sodium carbonatesolution. After the coupling is completed, the mixture is heated to70-80 C., and the dyestutf mixture is separated by the addition ofdilute hydrochloric acid and then filtered off. The paste thus obtainedis dissolved in 500 parts by volume of hot water with addition of dilutesodium hydroxide and treated at 80 C. with an ammoniacal solution of 8.5parts by weight of crystalline cobalt sulfate. The metal-containingdyestulf mixture is separated out by the addition of common salt,filtered off and dried. A brown powder is obtained which readilydissolves in water with a brown coloration and dyes wool from a neutralbath in intensely reddish brown shades of very good wet and lightfastness.

The corresponding mixed chromium complex dyes wool likewise in reddishbrown shades.

In a similar manner dyestuffs are produced from the diazo compounds andcoupling components listed in the following table.

Coupling com- Shade of Diazo component ponent Metal the dyeing,

on wool 19 l-amino-Z-hydroxy- N-butyM-hyd- Co Brick-red.

henzene-4-su1fonic roxy-2-quind acid amide. lone. 20 do .-do CrBlulsh-red. 21 1-amino-2-hydroxy- .do Or Do.

benzenei-sullonic acid dimethylamide. 22 1-amino-2-hydroxydo oBrick-red.

fi-methylbenzene 4-sulfonic acid amide. 23 l-amlnodhydroxy-N-methy1-4-hyd- 0o Blulsh-red.

benzene--sulfonic roxy-2quinolacid-o-a-uisidide. one. 241-amino-2-hydroxy- N-butyl-4-hy- Or Do.

benzene-s-methyldroxy-2-quinosuifone. lone. 25 l-amino-Z-hydroxy-N-phenyl-4-hy- Or Do.

benzene-fi-sulionic droxy-2-quinoacid amide. one. 26 1-amin0-2-hydroxy-N-butyl-4-hy- Or Do.

benzene-fi-ethyldroxy-2-quinosulfone. lone. 27 l-amino-Z-hydroxy-N-methyl-4hy- Or Do.

benzene-E-n-prodroxy-Z-quinopylsulione. lone. 1-amino-2-hydroxy-N-ethyM-hy- Or Do.

benzene--su1ion1c droxy-zquino- 1afid methylamlone.

e. do N-benzyM-hy- Or Do.

droxy-Z-qtfinolone.

I claim:

1. A metal complex compound selected from the group consisting of cobaltcomplexes and chromium complexes,

one mol of said metal being bound in complex union with 2 moles ofdyestuifs corresponding to the formula:

OH HO X l l X OH HO wherein X means a member selected from the groupconsisting of hydrogen and chlorine, R stands for a sulfonamide radicaland R means a lower alkyl radical, the dyestuffs being free of sulfonicand carboxylic acid groups.

3. A metal complex compound selected from the group consisting of cobaltcomplexes and chromium complexes, one mol of said metal being bound incomplex union with 2 mols of dyestuffs corresponding to the formula:

wherein X means a member selected from the group consisting of hydrogenand chlorine, R stands for a sulfonamide radical and R means a phenylradical, the dyestuffs being free of sulfonic and carboxylic acidgroups.

4. The cobalt complex of the monoazo dyestuif corresponding to theformula OH 11? BM kph I CH: C Bizi1 H2 5. The cobalt complex of themonoazo dyestufl corresponding to the formula OH HO OLHN: O

EHz-CHz-CHr-CH References Cited in the file of this patent UNITED STATESPATENTS

1. A METAL COMPLEX COMPOUND SELECTED FROM THE GROUP CONSISTING OF COBALTCOMPLEXES AND CHROMIUM COMPLEXES, ONE MOL OF SAID METAL BEING BOUND INCOMPLEX UNION WITH 2 MOLES OF DYESTUFFS CORRESPONDING TO THE FORMULA:WHEREIN X MEANS A MEMBER SELECTED FROM THE GROUP CONSISTING OF HYDROGENAND CHLORINE, R STANDS FOR A SULFONAMIDE RADICAL, AND R1 MEANS A MEMBERSELECTED FROM THE GROUP CONSISTING OF A -CH2-CH2-CH2- RADICAL LINKED TOTHE 8-POSITION AND A LOWER ALKYL, BENZYL AND PHENYL RADICAL, THEDYESTUFF BEING FREE OF SULFONIC AND CARBOXYLIC ACID GROUPS.